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Results for “Chemical calculations, Polarization”

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 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Full-Scale Ab Initio Simulation of Magic-Angle-Spinning Dynamic Nuclear Polarization

Theoretical models aimed at describing magic-angle-spinning (MAS) dynamic nuclear polarization (DNP) NMR have great potential in facilitating the in silico design of DNP polarizing agents and formulations. These models must typically face a trade-off between the accuracy of a strict quantum mechanical description and the need for using realistically large spin systems, for instance, using phenomenological models. In this paper, we show that the use of aggressive state-space restrictions and an optimization strategy allows full-scale ab initio MAS-DNP simulations of spin systems containing thousands of nuclei. Our simulations are shown to reproduce experimental DNP enhancements quantitatively, including their MAS rate dependence, for both frozen solutions and solid materials. They also reveal the importance of a previously unrecognized structural feature found in some polarizing agents that helps minimize the sensitivity losses imposed by the spin diffusion barrier.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

High-throughput computation of electric polarization in solids via Berry flux diagonalization

Electric polarization in the absence of an externally applied electric field is a key property of polar materials, but the standard interpolation-based ab initio approach to compute polarization differences within the modern theory of polarization presents challenges for automated high-throughput calculations. Berry flux diagonalization [J. Bonini et al., Phys. Rev. B 102, 045141 (2020)] has been proposed as an efficient and reliable alternative, though it has yet to be widely deployed. Here, we assess Berry flux diagonalization using ab initio calculations of a large set of materials, introducing and validating heuristics that ensure branch alignment with a minimal number of intermediate interpolated structures. Our automated implementation of Berry flux diagonalization succeeds in cases where prior interpolation-based workflows fail due to band-gap closures or branch ambiguities. Benchmarking with ab initio calculations of 176 candidate ferroelectrics, we demonstrate the efficacy of the approach on a broad range of insulating materials and obtain accurate effective polarization values with fewer interpolated structures than prior automated interpolation-based workflows. Our real-space heuristics that can predict gauge stability a priori from ionic displacements enable a general automated framework for reliable polarization calculations and efficient high-throughput screening of chemically and structurally diverse polar insulators. These results establish Berry flux diagonalization as a robust and efficient method to compute the effective polarization of solids and to accelerate the data-driven discovery of functional polar materials.

Poteshman, Abigail N. [University of Chicago, IL (↗
NASA NTRS1996

Stratospheric Heterogeneous Chemistry and Microphysics: Model Development, Validation and Applications

The objectives of this project are to: define the chemical and physical processes leading to stratospheric ozone change that involve polar stratospheric clouds (PSCS) and the reactions occurring on the surfaces of PSC particles; study the formation processes, and the physical and chemical properties of PSCS, that are relevant to atmospheric chemistry and to the interpretation of field measurements taken during polar stratosphere missions; develop quantitative models describing PSC microphysics and heterogeneous chemical processes; assimilate laboratory and field data into these models; and calculate the extent of chemical processing on PSCs and the impact of specific microphysical processes on polar composition and ozone depletion. During the course of the project, a new coupled microphysics/physical-chemistry/ photochemistry model for stratospheric sulfate aerosols and nitric acid and ice PSCs was developed and applied to analyze data collected during NASA's Arctic Airborne Stratospheric Expedition-II (AASE-II) and other missions. In this model, detailed treatments of multicomponent sulfate aerosol physical chemistry, sulfate aerosol microphysics, polar stratospheric cloud microphysics, PSC ice surface chemistry, as well as homogeneous gas-phase chemistry were included for the first time. In recent studies focusing on AASE measurements, the PSC model was used to analyze specific measurements from an aircraft deployment of an aerosol impactor, FSSP, and NO(y) detector. The calculated results are in excellent agreement with observations for particle volumes as well as NO(y) concentrations, thus confirming the importance of supercooled sulfate/nitrate droplets in PSC formation. The same model has been applied to perform a statistical study of PSC properties in the Northern Hemisphere using several hundred high-latitude air parcel trajectories obtained from Goddard. The rates of ozone depletion along trajectories with different meteorological histories are presently being systematically evaluated to identify the principal relationships between ozone loss and aerosol state. Under this project, we formulated a detailed quantitative model that predicts the multicomponent composition of sulfate aerosols under stratospheric conditions, including sulfuric, nitric, hydrochloric, hydrofluoric and hydrobromic acids. This work defined for the first time the behavior of liquid ternary-system type-1b PSCS. The model also allows the compositions and reactivities of sulfate aerosols to be calculated over the entire range of environmental conditions encountered in the stratosphere (and has been incorporated into a trajectory/microphysics model-see above). Important conclusions that derived from this work over the last few years include the following: the HNO3 content of liquid-state aerosols dominate PSCs below about 195 K; the freezing of nitric acid ice from sulfate aerosol solutions is likely to occur within a few degrees K of the water vapor frost point; the uptake and reactions of HCl in liquid aerosols is a critical component of PSC heterogeneous chemistry. In a related application of this work, the inefficiency of chlorine injection into the stratosphere during major volcanic eruptions was explained on the basis of nucleation of sulfuric acid aerosols in rising volcanic plumes leading to the formation of supercooled water droplets on these aerosols, which efficiently scavenges HCl via precipitation.

Turco, Richard P.↗
DOE OSTI2023

Signatures of Non-universal Quantum Dynamics of Ultracold Chemical Reactions of Polar Alkali Dimer Molecules with Alkali Metal Atoms: Li( 2 S) + NaLi( a 3 Σ + ) → Na( 2 S) + Li 2 ( a 3 Σ u + )

Ultracold chemical reactions of weakly bound triplet-state alkali metal dimer molecules have recently attracted much experimental interest. Here we perform rigorous quantum scattering calculations with a new ab initio potential energy surface to explore the chemical reaction of spin-polarized NaLi(a 3 Σ + ) and Li( 2 S) to form Li 2 (a 3 Σ u + ) and Na( 2 S). The reaction is exothermic and proceeds readily at ultralow temperatures. Significantly, we observe strong sensitivity of the total reaction rate to small variations of the three-body part of the Li 2 Na interaction at short range, which we attribute to a relatively small number of open Li 2 (a 3 Σ u + ) product channels populated in the reaction. This provides the first signature of highly non-universal dynamics seen in rigorous quantum reactive scattering calculations of an ultracold exothermic insertion reaction involving a polar alkali dimer molecule, opening up the possibility of probing microscopic interactions in atom+molecule collision complexes via ultracold reactive scattering experiments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1998

EOS Interdisciplinary Investigation: Observational and Modeling Studies of Radiative, Chemical, and Dynamical Interactions in the Earth's Atmosphere

A 3-dimensional model of atmospheric dynamics and photochemistry has been developed from the primitive equations in isentropic coordinates. The model extends from the upper troposphere through the middle atmosphere and is driven by observed dynamical and chemical structure in the troposphere. The model's formulation is entirely spectral: Horizontal structure is represented in terms of vector Hough functions, which explicitly partition the motion into its rotational and divergent components. This formulation enables the model's computational performance to be increased dramatically by filtering high-frequency gravity waves, which do not affect PV conservation. Vertical structure is represented in terms of eigenfunctions that follow from the primitive equations in isentropic coordinates. The model's fully spectral formulation enables scale-selective dissipation, necessary for numerical stability, to be applied at 6th order-in all 3 coordinate directions. This feature leaves all but the shortest vertical scales undamped and, consequently, allows potential vorticity and chemical tracers to be conserved quite accurately, distinctly better than in the model's layered counterpart. These dynamical features are complemented by a basic but fairly complete treatment of gas phase photochemistry, which accounts for some 48 chemical species, diurnally-varying SW absorption by O2 and O3, and LW cooling calculated via a detailed band calculation of radiative transfer. Driven by observed tropospheric structure, the 3D model reproduces observed structure in the middle atmosphere, inclusive of transport by the Brewer-Dobson circulation and accompanying chemical variations. Calculated residual motion is consistent with diabatic cooling rates, poleward transport, and descent in the polar night derived from satellite measurements of chemical tracers made from LIMS, SAGE, and UARS. The model also reproduces the observed structure of chemical species like O3, HNO3, and ClO. At the same time, it provides a respectable 3D simulation of the wintertime increase of midlatitude total ozone, as well as its geographical structure observed by Nimbus-7 TOMS. The 3D model has been used to explore the origin of diabatic upwelling in the tropical lower stratosphere, which has been related to planetary wave absorption in the winter- time stratosphere, as well as to influences from tropospheric convection at the tropical tropopause.

Salby, Murry L.↗
DOE OSTI2023

Solvent Induced Proton Polarization within the Nuclear–Electronic Orbital Framework

To explicitly account for nuclear quantum effects and solvent environments in simulations of chemical processes, the nuclear-electronic orbital approach is coupled with a polarizable continuum model (PCM). This NEO–PCM approach is used to explore the influence of solvation on nuclear polarization through applications to a water dimer and a set of protonated water tetramers. Nuclear polarization in these species is analyzed in terms of changes in proton density and oxygen–hydrogen bond length. Solvation is shown to enhance nuclear polarization with increasing dielectric constant. For the water dimer, the internal, hydrogen-bonded proton is shown to polarize more than the external, free proton. Moreover, proton quantization leads to greater solvent polarization through their mutual polarization. Furthermore, these calculations highlight the complex interplay among electronic, nuclear, and solvent polarization in chemical systems.

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

Computational and experimental study of different brines in temperature swing solvent extraction desalination with amine solvents

Rapid global urbanization and high-salinity wastewater disposal from industrial activities have exerted significant pressure on water resources. Over the past few years, temperature swing solvent extraction (TSSE) has been identified as a promising technique to desalinate hypersaline brines. Despite its potential, the TSSE desalination literature has been mainly based on empirical insights, and the limited molecular simulation studies have primarily focused on NaCl brines. Herein, we use molecular dynamics (MD) simulations to study the TSSE desalination of four different brines, namely, KCl, KBr, NaCl, and NaBr using diisopropylamine as the solvent. Based on both bulk and interfacial brine-diisopropylamine MD results, here we investigate the qualitative and quantitative performance of the simulations by benchmarking these results against our experimental evaluations of these same systems. MD results provide satisfactory qualitative agreement with the experimental data of water solubilization in the organic phase and amine solubilization in the aqueous phase for the KBr, KCl, and NaBr brines. Also, the molecular mechanism of solvation of ionic species by water molecules over diisopropylamine suggested by the MD simulations is in agreement with our experimental data. However, larger qualitative and quantitative deviations were observed for the NaCl brines, and this is likely due to polarization and charge transfer effects, as quantified by our quantum chemical calculations.

42 ENGINEERING↗
DOE OSTI2022

Numerical Simulation of Vibrational Sum Frequency Generation Intensity for Non-Centrosymmetric Domains Interspersed in an Amorphous Matrix: A Case Study for Cellulose in Plant Cell Wall

Vibrational sum frequency generation (SFG) spectroscopy can specifically probe molecular species non-centrosymmetrically arranged in a centrosymmetric or isotropic medium. This capability has been extensively utilized to detect and study molecular species present at the two-dimensional (2D) interface at which the centrosymmetry or isotropy of bulk phases is naturally broken. The same principle has been demonstrated to be very effective for the selective detection of non-centrosymmetric crystalline nanodomains interspersed in three-dimensional (3D) amorphous phases. However, the full spectral interpretation of SFG features has been difficult due to the complexity associated with the theoretical calculation of SFG responses of such 3D systems. This paper describes a numerical method to predict the relative SFG intensities of non-centrosymmetric nanodomains in 3D systems as functions of their size and concentration as well as their assembly patterns, i.e., the distributions of tilt, azimuth, and rotation angles with respect to the lab coordinate. We applied the developed method to predict changes in the CH and OH stretch modes characteristic to crystalline cellulose microfibrils distributed with various orders, which are relevant to plant cell wall structures. As a result, the same algorithm can also be applied to any SFG-active nanodomains interspersed in 3D amorphous matrices.

36 MATERIALS SCIENCE↗
NASA NTRS1991

Spatial and temporal variability of the extent of chemically processed stratospheric air

Simulations of the spatial and temporal variability of the extent of chemically processed air in the Arctic stratosphere have been carried out using a three-dimensional chemistry-transport model for the winters of 1979 and 1989. Chemically processed air is identified in the model as that in which the amounts of hydrogen chloride (HCl) calculated with parameterized loss for conditions appropriate to polar stratospheric cloud (PSC) formation are substantially smaller than those calculated in a model with gas phase chemistry only. It is seen that chemically processed air may be identified over much of the Arctic lower stratosphere from early January to late February, with HCl depletions being larger in 1989 than in 1979. Near the latitude of the Arctic circle, there is important spatial and temporal variability in the extent of chemically processed air. There is some evidence for transport to midlatitudes of processed air during these winters, but the HCl reductions are much smaller and more sporadic than those near the pole. At 62 and 42N, processed air is calculated to occur preferentially over the longitude regions from 60-120E and 270-330E.

Kaye, Jack A.↗
NASA NTRS1990

Theoretical predictions

In order to understand the impact of man made chemicals on the atmospheric ozone layer, it is essential to develop models that can perform long term predictions of future ozone changes. An advantage of using two dimensional models is that they can be used to predict latitudinal and seasonal changes in ozone. The formulation and recent improvements are described in 2-D models, which are used herein, along with the three dimensional models that are currently being developed to better simulate transport of chemically active trace gases, especially in polar regions. The range in 2-D model calculations is described. Selected fields calculated by these models are compared with observations. A number of scenarios have been defined, which encompass possible emission rates of different halocarbons. Because of the large uncertainties in the rates for heterogeneous processes, the calculated responses of the models include only the effects of homogeneous chemistry. One important distinction among the models is their ability to account for temperature feedbacks on the calculated ozone changes.

Brasseur, G.↗
NASA NTRSDate not supplied

An Examination of Autumn Southern Polar Ozone Tendencies and the Residual Circulation in MERRA-2 Products

Changes in lower stratospheric ozone caused by dynamical transport can be difficult to characterize and thus are sometimes difficult to distinguish from chemical losses. Correlations between ozone changes and various dynamical proxies (e.g., the eddy heat flux) from year to year can be of interest, but they do little in themselves to explain the ozone transport mechanisms behind such correlations. In this study, we use products from the Modern-Era Retrospective analysis for Research and Applications Version 2 (MERRA-2) to calculate the ozone mass flux, integrating it in space and time over the upper tropospheric/lower stratospheric Southern polar cap during periods when little chemical loss is expected. The ozone mass flux is expressed in terms of components of the residual circulation of the Transformed Eulerian Mean (TEM, i.e., 𝑣𝑣̅ ∗and 𝑤𝑤(∗) as well as eddy mixing terms. We relate these terms to the local ozone mass tendency ("#! "$ ), similarly integrated, and we find that the interannual variability of the ozone changes are strongly related to the residual meridional circulation and the meridional eddy mixing terms. These directly calculated dynamical transport terms provide clearer ozone proxies. Removing these advective terms from a long-term ozone time series can more effectively reveal ozone variations and long-term trends, specifically those caused by photochemical production and losses (e.g., human-produced ozone depletion).

Ozone↗
NASA NTRS2012

Characterization of the Morphometry of Impact Craters Hosting Polar Deposits in Mercury's North Polar Region

Earth-based radar images dating back two decades show that the floors of some polar craters on Mercury host radar-bright deposits that have been proposed to consist of frozen volatiles. Several hypotheses have been put forth to explain their source, including volcanic outgassing, chemical sputtering, and deposition of exogenous water ice. Calculations show that volatiles are thermally stable in permanently shadowed areas. An earlier study of the depths of north polar craters determined with photoclinometric techniques applied to Mariner 10 images yielded the conclusion that the mean ratio of crater depth d to rim-crest diameter D for craters hosting polar deposits is two-thirds that of the mean ratio for a comparable population of neighboring craters lacking such deposits. This result could be explained by (though doesn't require) the presence of a thick layer of volatiles within the polar deposit-hosting craters. Here we use altimetric profiles and topographic maps obtained by the Mercury Laser Altimeter (MLA) to revisit this analysis. MLA is an instrument on the MErcury Surface, Space ENvironment, GEochemistry, and Ranging (MESSENGER) spacecraft, which has been orbiting Mercury since March 2011. MLA transmits a 1064-nm laser pulse at 8 Hz during MESSENGER's trajectory over Mercury s surface. The MLA illuminates surface areas averaging between 15 m and 100 m in diameter, spaced approx 400 m apart along the spacecraft ground track. The radial precision of individual measurements is <1 m, and the current accuracy with respect to Mercury s center of mass is better than 20 m. As of mid-December 2011, MLA coverage had reached to 15 S and has yielded a comprehensive map of the topography of Mercury s northern hemisphere. The MLA data are used here to quantify the shapes of craters in the north polar region and to avoid the shadowing bias of photoclinometric techniques.

Talpe, Matthieu, J.↗
DOE OSTI2025

Proximity ferroelectricity in wurtzite heterostructures

Proximity ferroelectricity is an interface-associated phenomenon in electric-field-driven polarization reversal in a non-ferroelectric polar material induced by one or more adjacent ferroelectric materials. Here, in this paper, we report proximity ferroelectricity in wurtzite ferroelectric heterostructures. In the present case, the non-ferroelectric layers are AlN and ZnO, whereas the ferroelectric layers are Al 1−x B x N, Al 1−x Sc x N and Zn 1−x Mg x O. The layered structures include nitride–nitride, oxide–oxide and nitride–oxide stacks that feature two-layer (asymmetric) and three-layer (symmetric) configurations. Ferroelectric switching in both layers is validated by multimodal characterization methods, including polarization hysteresis, anisotropic chemical etching, second harmonic generation, piezo response force microscopy, electromechanical testing and atomic resolution polarization orientation imaging in real space by scanning transmission electron microscopy. We present a physical switching model in which antipolar nuclei originate in the ferroelectric layer and propagate towards the internal non-ferroelectric interface. The domain wall leading edge produces elastic and electric fields that extend beyond the interface at close proximity, reducing the switching barrier in the non-ferroelectric layer, and allowing complete domain propagation without breakdown. Density functional theory calculations of polymorph energies, reversal barriers and domain wall energies support this model. Proximity ferroelectricity enables polarization reversal in wurtzites without the chemical or structural disorder that accompanies elemental substitution, opening new questions and opportunities regarding interface-based ferroelectricity.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Dynamics of Aqueous Electrolyte Solutions: Challenges for Simulations

This Perspective article focuses on recent simulation work on the dynamics of aqueous electrolytes. It is well-established that full-charge, nonpolarizable models for water and ions generally predict solution dynamics that are too slow in comparison to experiments. Models with reduced (scaled) charges do better for solution diffusivities and viscosities but encounter issues describing other dynamic phenomena such as nucleation rates of crystals from solution. Polarizable models show promise, especially when appropriately parametrized, but may still miss important physical effects such as charge transfer. First-principles calculations are starting to emerge for these properties that are in principle able to capture polarization, charge transfer, and chemical transformations in solution. Finally, while direct ab initio simulations are still too slow for simulations of large systems over long time scales, machine-learning models trained on appropriate first-principles data show significant promise for accurate and transferable modeling of electrolyte solution dynamics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1992

Natural and anthropogenic perturbations of the stratospheric ozone layer

The paper reviews potential causes for reduction in the ozone abundance. The response of stratospheric ozone to solar activity is discussed. Ozone changes are simulated in relation with the potential development of a fleet of high-speed stratospheric aircraft and the release in the atmosphere of chlorofluorocarbons. The calculations are performed by a two-dimensional chemical-radiative-dynamical model. The importance of heterogeneous chemistry in polar stratospheric clouds and in the Junge layer (sulfate aerosol) is emphasized. The recently reported ozone trend over the last decade is shown to have been largely caused by the simultaneous effects of increasing concentrations of chlorofluorocarbons and heterogeneous chemistry. The possibility for a reduction in stratospheric ozone following a large volcanic eruption such as that of Mount Pinatubo in 1991 is discussed.

Brasseur, Guy P.↗
NASA NTRS1993

Heterogeneous chemistry on Antarctic polar stratospheric clouds - A microphysical estimate of the extent of chemical processing

A detailed model of polar stratospheric clouds (PSCs), which includes nucleation, condensational growth. and sedimentation processes, has been applied to the study of heterogeneous chemical reactions. For the first time, the extent of chemical processing during a polar winter has been estimated for an idealized air parcel in the Antarctic vortex by calculating in detail the rates of heterogeneous reactions on PSC particles. The resulting active chlorine and NO(x) concentrations at first sunrise are analyzed with respect to their influence upon the Antarctic ozone hole using a photochemical model. It is found that the species present at sunrise are primarily influenced by the relative values of the heterogeneous reaction rate constants and the initial gas concentrations. However, the extent of chlorine activation is also influenced by whether N2O5 is removed by reaction with HCl or H2O. The reaction of N2O5 with HCl, which occurs rapidly on type 1 PSCs, activates the chlorine contained in the reservoir species HCl. Hence the presence and surface area of type 1 PSCs early in the winter are crucial in determining ozone depletion.

Drdla, K.↗
DOE OSTI2021

Electron–Nucleus Hyperfine Coupling Calculated from Restricted Active Space Wavefunctions and an Exact Two-Component Hamiltonian

Exact two-component (X2C) relativistic nuclear hyperfine magnetic field operators were incorporated in X2C ab-initio wavefunction calculations at the multi-reference restricted active space (RAS) level for calculations of nuclear hyperfine magnetic properties. Spin-orbit coupling was treated via RAS state interaction (SO-RASSI). The method was tested by calculations of electron – nucleus hyperfine coupling constants. The approach, implemented in the OpenMolcas program, overcomes a major limitation of a previous SO-RASSI implementation for hyperfine coupling that relied on non-relativistic hyperfine operators [J. Chem. Theor. Comput. 2015, 11, 538–549] and therefore had only limited applicability. Furthermore, results from calculations on systems with light and heavy main group elements, transition metals, lanthanides, and one actinide complex, demonstrate reasonably good agreement with experimental data, where available, as long as the active space can generate sufficient spin polarization.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1993

A model for heterogeneous chemical processes on the surfaces of ice and nitric acid trihydrate particles

The study presents a model that incorporates the physics and physical chemistry of ice surfaces relevant to polar stratospheric clouds. Surface concentrations of H2O, HCl, HOCl, ClONO2, and N2O5 on ice and nitric acid trihydrate (NAT) crystals are computed, and surface reaction rates and reaction probabilities (sticking coefficients) are determined. For gas pressures of about 10 exp -7 torr and temperatures in the range of 180-200 K, HCl completely coats ice and water-rich NAT surfaces, while HOCl, ClOHO2, and N2O5 may cover 0.01-1 percent of these surfaces. The energy parameters are used to calculate surface temperatures such as adsorption and desorption constants, surface coverages, reaction rate coefficients, surface diffusion coefficients, and reaction probabilities for various species and chemical interactions on ice and NAT surfaces. Implications for chemical processing on polar stratospheric clouds are discussed.

Tabazadeh, Azadeh↗