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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 307 records · Page 17
All sourcesNASA NTRSDOE OSTI
NASA NTRSDate not supplied

NASA's High-Resolution GEOS Forecasting and Reanalysis Products: A Unified Tool from Local to Global Scales

NASA's GMAO produces high-resolution global forecasts for weather, aerosols, and air quality. The NASA Global Earth Observing System (GEOS) model has been expanded to provide global near-real-time 5-day forecasts of atmospheric chemical composition at unprecedented horizontal resolution of 0.25 degrees (~25 km), freely available to the public. This composition forecast system (GEOS-CF) combines the operational GEOS weather forecasting model with the state-of-the-science GEOS-Chem chemistry module to provide detailed analysis of a wide range of air pollutants such as ozone, carbon monoxide, nitrogen oxides, and fine particulate matter (PM2.5). GEOS-CF also assimilated satellite observations into the system for improved representation of weather and smoke. The assimilation system is currently being expanded to include chemically reactive trace gases. While the main focus of this new product is on tropospheric air quality information, the GEOS-Chem chemistry model used in this system includes the unified tropospheric stratospheric chemistry mechanism for improved forecasts of total column ozone during anomalous dynamical and chemical events. I will discuss current capabilities of the GEOS Constituent Data Assimilation System (CoDAS) to improve atmospheric composition modeling and possible future directions for GEOS-CF and reanalysis products. In addition, I will show how machine learning techniques can be used to correct for sub-grid-scale variability, which further improves model estimates at a given observation site.

Co-DAS↗
DOE OSTI2026

A Chemodynamical Census of the Milky Way's Ultra-Faint Compact Satellites. I. A First Population-Level Look at the Internal Kinematics and Metallicities of 19 Extremely-Low-Mass Halo Stellar Systems

Deep, wide-area photometric surveys have uncovered a population of compact ($r_{1/2} \approx$ 1-15 pc), extremely-low-mass ($M_* \approx$ 20-4000 $M_{\odot}$) stellar systems in the Milky Way halo that are smaller in size than known ultra-faint dwarf galaxies (UFDs) and substantially fainter than most classical globular clusters (GCs). Very little is known about the nature and origins of this population of "Ultra-Faint Compact Satellites" (UFCSs) owing to a dearth of spectroscopic measurements. Here, we present the first spectroscopic census of these compact systems based on Magellan/IMACS and Keck/DEIMOS observations of 19 individual UFCSs, representing $\sim$2/3 of the known population. We securely measure mean radial velocities for all 19 systems, velocity dispersions for 15 (predominantly upper limits), metallicities for 17, metallicity dispersions for 8, and $\textit{Gaia}$-based mean proper motions for 18. This large new spectroscopic sample provides the first insights into population-level trends for these extreme satellites. We demonstrate that: (1) the UFCSs are kinematically colder, on average, than the UFDs, disfavoring very dense dark matter halos in most cases, (2) the UFCS population is chemically diverse, spanning a factor of $\sim$300 in mean iron abundance ($\rm -3.3 \lesssim [Fe/H] \lesssim -0.8$), with multiple systems falling beneath the "metallicity floor" proposed for GCs, and (3) while some higher-metallicity and/or younger UFCSs are clearly star clusters, the dynamical and/or chemical evidence allows the possibility that up to $\sim$50% of the UFCSs in our sample (9 of 19) may represent the smallest and least-massive galaxies yet discovered.

Cerny, William [Yale U.] (ORCID:0000000316977062)↗
DOE OSTI2024

Uncovering fast solid-acid proton conductors based on dynamics of polyanion groups and proton bonding strength

Achieving high proton conductivity in inorganic solids is key for advancing many electrochemical technologies, including low-energy nano-electronics and energy-efficient fuel cells and electrolyzers. A quantitative understanding of the physical traits of a material that regulate proton diffusion is necessary for accelerating the discovery of fast proton conductors. In this work, we have mapped the structural, chemical and dynamic properties of solid acids to the elementary steps of the Grotthuss mechanism of proton diffusion. Our approach combines ab initio molecular dynamics simulations, analysis of phonon spectra and atomic structure calculations. We have identified the donor–hydrogen bond lengths and the acidity of polyanion groups as key descriptors of local proton transfer and the vibrational frequencies of the cation framework as the key descriptor of lattice flexibility. The latter facilitates rotations of polyanion groups and long-range proton migration in solid acid proton conductors. The calculated lattice flexibility also correlates with the experimentally reported superprotonic transition temperatures. Using these descriptors, we have screened the Materials Project database and identified potential solid acid proton conductors with monovalent, divalent and trivalent cations, including Ag + , Sr 2+ , Ba 2+ and Er 3+ cations, which go beyond the traditionally considered monovalent alkali cations (Cs + , Rb + , K + , and NH 4 + ) in solid acids.

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

Strictly non-adiabatic quantum control of the acetylene dication using an infrared field

We demonstrate the existence of a strictly non-adiabatic control pathway in deprotonation of the acetylene dication. This pathway is identified experimentally by measuring a kinetic energy shift in an ion coincidence experiment. We use a time dependent Schrödinger equation simulation to identify which properties most strongly affect our control. We find that resonant control around conical intersections is limited by the speed of non-adiabatic dynamics.

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

Excited-state dynamics of CH 2 I 2 and CH 2 IBr studied with UV-pump VUV-probe momentum-resolved photoion spectroscopy

We perform time-resolved ionization spectroscopy measurements of the excited state dynamics of CH 2 I 2 and CH 2 IBr following photoexcitation in the deep UV. The fragment ions produced by ionization with a vacuum-ultraviolet probe pulse are measured with velocity map imaging, and the momentum resolved yields are compared with trajectory surface hopping calculations of the measurement observable. Together with recent time-resolved photoelectron spectroscopy measurements of the same dynamics, these results provide a detailed picture of the coupled electronic and nuclear dynamics involved. Overall, our measurements highlight the non-adiabatic coupling between electronic states, which leads to notable differences in the dissociation dynamics for the two molecules.

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

Mapping wave packet bifurcation at a conical intersection in CH 3 I by attosecond XUV transient absorption spectroscopy

Extreme ultraviolet (XUV) transient absorption spectroscopy has emerged as a sensitive tool for mapping the real-time structural and electronic evolution of molecules. Here, attosecond XUV transient absorption is used to track dynamics in the A-band of methyl iodide (CH 3 I). Gaseous CH 3 I molecules are excited to the A-band by a UV pump (277 nm, ~20 fs) and probed by attosecond XUV pulses targeting iodine I(4d) core-to-valence transitions. Owing to the excellent temporal resolution of the technique, passage through a conical intersection is mapped through spectral signatures of nonadiabatic wave packet bifurcation observed to occur at 15 ± 4 fs following UV photoexcitation. The observed XUV signatures and time dynamics are in agreement with previous simulations [H. Wang, M. Odelius, and D. Prendergast, J. Chem. Phys. 151, 124106 (2019)]. Furthermore, due to the short duration of the UV pump pulse, coherent vibrational motion in the CH 3 I ground state along the C-I stretch mode (538 ± 7 cm -1 ) launched by resonant impulsive stimulated Raman scattering and dynamics in multiphoton excited states of CH 3 I are also detected.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Verification and validation of detonation-shock-dynamics relations for explosives described by general equation of state and chemical reaction models

Detonation shock dynamics is a powerful method to model the behaviour of High Explosives (HE). However in order to use this method, the underlying relationship between the local radius of curvature and the detonation speed must be known. Previous work has developed methods to calculate this effect using simple, single-step Arrhenius and polytropic gas, models for the chemical reaction and the equation of state, respectively. In recent years, more complex models for both reaction rates and equations of state have been developed which show better agreement with experimental data than these simple models, especially when considering condensed phase explosives.. This work presents the governing equations for solving these problems in a way that is generalised to use arbitrary equations of state as well as reaction models which may have more than a single step and multiple product species. This implementation is verified against exact solutions, demonstrating that the equations were implemented properly. The verified algorithm is then validated against experimental data and high fidelity simulations, showing that it is able to make accurate predictions in a regime where the underlying assumptions of the governing equations are valid. Importantly, this approach has many applications: from creating equivalent detonation shock dynamics models for existing reactive burn calibrations for HE; to developing new functional forms and calibrations of reactive burn models for condensed phase high explosives.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1995

Vertical structure of the midlatitude temperature from stratosphere to mesopause (30 - 105 km)

Data sets from Rayleigh lidar (1979-93) at the Observatory of Haute-Provence (44 deg N, 6 deg E) and at Biscarrosse (44 deg N, 1 deg W) of southern France, and from narrowband Na lidar (1991-4) at Fort Collins, Colorado (41 deg N, 105 deg W) are used to deduce the vertical temperature structure of the midlatitude middle atmosphere from 30 - 105 km. Nightly averaged temperatures measured across the Atlantic at comparable latitudes between 81 and 90 km showed seasonal variations tracking one another. Harmonic analyses of the measured profiles at these sites have been compared to the reference atmosphere, CIRA 1986. Considerable differences are noted in the annual mean temperautres in the mesopause region. Two temperature minima at 86 and 99 m are observed, suggesting heating and cooling mechnanisms not previously incorporated into the reference atmosphere. Using the new 3D TIME-General Circulation Model (GCM) of Roble and Ridley which includes both dynamical and chemical processes, we account for this anomalous behavior by model simulation for the first time. Except the existence of strong semi-annual oscillations, the observed annual and semi-annual temperature variations are compatible with CIRA 1986. Observed annual temperature and solar flux forcing are out-of-phase between 65 and 99 km, reflecting dynamics dominated atmosphere at these altitudes.

She, C. Y.↗
DOE OSTI2024

QRCODE: Massively parallelized real-time time-dependent density functional theory for periodic systems

We present a new software module, QRCODE (Quantum Research for Calculating Optically Driven Excitations), for massively parallelized real-time time-dependent density functional theory (RT-TDDFT) calculations of periodic systems in the open-source Qbox software package. Our approach utilizes a custom implementation of a fast Fourier transformation scheme that significantly reduces inter-node message passing interface (MPI) communication of the major computational kernel and shows impressive scaling up to 16,344 CPU cores. In addition to improving computational performance, QRCODE contains a suite of various time propagators for accurate RT-TDDFT calculations. As benchmark applications of QRCODE, we calculate the current density and optical absorption spectra of hexagonal boron nitride (h-BN) and photo-driven reaction dynamics of the ozone-oxygen reaction. We also calculate the second and higher harmonic generation of monolayer and multi-layer boron nitride structures as examples of large material systems. Our optimized implementation of RT-TDDFT in QRCODE enables large-scale calculations of real-time electron dynamics of chemical and material systems with enhanced computational performance and impressive scaling across several thousand CPU cores.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2024

Non-equilibrium rate theory for polariton relaxation dynamics

We derive an analytic expression of the non-equilibrium Fermi’s golden rule (NE-FGR) expression for a Holstein–Tavis–Cumming Hamiltonian, a universal model for many molecules collectively coupled to the optical cavity. These NE-FGR expressions capture the full-time-dependent behavior of the rate constant for transitions from polariton states to dark states. The rate is shown to be reduced to the well-known frequency domain-based equilibrium Fermi’s golden rule (E-FGR) expression in the equilibrium and collective limit and is shown to retain the same scaling with the number of sites in non-equilibrium and non-collective cases. We use these NE-FGR to perform population dynamics with a time-non-local and time-local quantum master equation and obtain accurate population dynamics from the initially occupied upper or lower polariton states. Furthermore, NE-FGR significantly improves the accuracy of the population dynamics when starting from the lower polariton compared to the E-FGR theory, highlighting the importance of the non-Markovian behavior and the short-time transient behavior in the transition rate constant.

Chemical dynamics↗
DOE OSTI2020

Real-space formulation of the stress tensor for O (N) density functional theory: Application to high temperature calculations

We present an accurate and efficient real-space formulation of the Hellmann–Feynman stress tensor for O (N) Kohn–Sham density functional theory (DFT). While applicable at any temperature, the formulation is most efficient at high temperature where the Fermi–Dirac distribution becomes smoother and the density matrix becomes correspondingly more localized. We first rewrite the orbital-dependent stress tensor for real-space DFT in terms of the density matrix, thereby making it amenable to O (N) methods. We then describe its evaluation within the O (N) infinite-cell Clenshaw–Curtis Spectral Quadrature (SQ) method, a technique that is applicable to metallic and insulating systems, is highly parallelizable, becomes increasingly efficient with increasing temperature, and provides results corresponding to the infinite crystal without the need of Brillouin zone integration. We demonstrate systematic convergence of the resulting formulation with respect to SQ parameters to exact diagonalization results and show convergence with respect to mesh size to the established plane wave results. Here, we employ the new formulation to compute the viscosity of hydrogen at 10 6 K from Kohn–Sham quantum molecular dynamics, where we find agreement with previous more approximate orbital-free density functional methods.

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

Nonadiabatic transition paths from quantum jump trajectories

We present a means of studying rare reactive pathways in open quantum systems using transition path theory and ensembles of quantum jump trajectories. This approach allows for the elucidation of reactive paths for dissipative, nonadiabatic dynamics when the system is embedded in a Markovian environment. Here, we detail the dominant pathways and rates of thermally activated processes and the relaxation pathways and photoyields following vertical excitation in a minimal model of a conical intersection. We find that the geometry of the conical intersection affects the electronic character of the transition state as defined through a generalization of a committor function for a thermal barrier crossing event. Similarly, the geometry changes the mechanism of relaxation following a vertical excitation. Relaxation in models resulting from small diabatic coupling proceeds through pathways dominated by pure dephasing, while those with large diabatic coupling proceed through pathways limited by dissipation. The perspective introduced here for the nonadiabatic dynamics of open quantum systems generalizes classical notions of reactive paths to fundamentally quantum mechanical processes.

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

Time evolution of ML-MCTDH wavefunctions. II. Application of the projector splitting integrator

The multi-layer multi-configuration time-dependent Hartree (ML-MCTDH) approach can suffer from numerical instabilities whenever the wavefunction is weakly entangled. These instabilities arise from singularities in the equations of motion (EOMs) and necessitate the use of regularization of the EOMs. The Projector Splitting Integrator (PSI) has previously been presented as an approach for evolving ML-MCTDH wavefunctions that is free of singularities. Here, we will discuss the implementation of the multi-layer PSI with a particular focus on how the steps required relate to those required to implement standard ML-MCTDH. We demonstrate the efficiency and stability of the PSI for large ML-MCTDH wavefunctions containing up to hundreds of thousands of nodes by considering a series of spin-boson models with up to 106 bath modes and find that for these problems, the PSI requires roughly 3–4 orders of magnitude fewer Hamiltonian evaluations and 2–3 orders of magnitude fewer Hamiltonian applications than standard ML-MCTDH and 2–3/1–2 orders of magnitude fewer evaluations/applications than approaches that use improved regularization schemes. Finally, we consider a series of significantly more challenging multi-spin-boson models that require much larger numbers of single-particle functions with wavefunctions containing up to ~1.3×10 9 parameters to obtain accurate dynamics.

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

Capture and Decomposition of the Nerve Agent Simulant, DMCP, Using the Zeolitic Imidazolate Framework (ZIF-8)

Understanding mechanisms of decontamination of chemical warfare agents (CWA) is an area of intense research aimed at developing new filtration materials to protect soldiers and civilians in case of state-sponsored or terrorist attack. In this study, we employed complementary structural, chemical, and dynamic probes and in situ data collection, to elucidate the complex chemistry, capture, and decomposition of the CWA simulant, dimethyl chlorophosphonate (DMCP). Our work reveals key details of the reactive adsorption of DMCP and demonstrates the versatility of zeolitic imidazolate framework (ZIF-8) as a plausible material for CWA capture and decomposition. Here, the in situ synchrotron-based powder X-ray diffraction (PXRD) and pair distribution function (PDF) studies, combined with Fourier transform infrared (FT-IR) spectroscopy, X-ray photoelectron spectroscopy (XPS), zinc K-edge X-ray absorption near edge structure (XANES), and Raman spectroscopies, showed that the unique structure, chemical state, and topology of ZIF-8 enable accessibility, adsorption, and hydrolysis of DMCP into the pores and revealed the importance of linker chemistry and Zn 2+ sites for nerve agent decomposition. DMCP decontamination and decomposition product(s) formation were observed by thermogravimetric analysis, FT-IR spectroscopy, and phosphorus (P) K-edge XANES studies. Differential PDF analysis indicated that the average structure of ZIF-8 (at the 30 Å scale) remains unchanged after DMCP dosing and provided information on the dynamics of interactions of DMCP with the ZIF-8 framework. Using in situ PXRD and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), we showed that nearly 90% regeneration of the ZIF-8 structure and complete liberation of DMCP and decomposition products occur upon heating.

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

Geometric phase in coupled cluster theory

It has been well-established that the topography around conical intersections between excited electronic states is incorrectly described by coupled cluster and many other single reference theories (the intersections are “defective”). Despite this, we show both analytically and numerically that the geometric phase effect (GPE) is correctly reproduced upon traversing a path around a defective excited-state conical intersection (CI) in coupled cluster theory. The theoretical analysis is carried out by using a non-Hermitian generalization of the linear vibronic coupling approach. Interestingly, the approach qualitatively explains the characteristic (incorrect) shape of the defective CIs and CI seams. Moreover, the validity of the approach and the presence of the GPE indicate that defective CIs are local (and not global) artifacts. This implies that a sufficiently accurate coupled cluster method could predict nuclear dynamics, including geometric phase effects, as long as the nuclear wavepacket never gets too close to the conical intersections.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRSDate not supplied

Composition Reanalyses at NASA’s Global Modeling and Assimilation Office

Scientific Assessments of Ozone Depletion 2018 and 2022 report the recovery of Antarctic ozone, consistent with diminishing concentrations of halogens in the stratosphere. Both the size and the depth of the springtime ozone holes exhibit downward trends, particularly in September. Superimposed on the recovery trend are significant year-to-year fluctuations arising from dynamical variability potentially influenced by climate forcing and volcanic eruptions. Since 2018 the Antarctic stratosphere has experienced a wild parade of austral spring seasons with a sudden stratospheric warming and exceptionally high ozone in 2019 followed by large and long-lasting ozone holes in the following years, prompting questions about the speed and detectability of Antarctic ozone recovery and its potential connections to human-induced climate change. From the Australian New Years’ wildfires of 2020 to volcanic aerosols to the unprecedented injection of water vapor by the Hunga volcanic eruption, recent scientific literature on the subject investigates many factors that may or may not have contributed to this remarkable interannual variability. This presentation summarizes dynamical influences on springtime Antarctic stratospheric ozone in recent years and discusses these results in the context of long-term trends. In particular, this work seeks to isolate dynamical and chemical contributions to the Antarctic springs since 2019 using a consistent methodological framework. Our analysis uses constituent and meteorological fields from the MERRA-2 Stratospheric Composition Reanalysis of Aura MLS (M2-SCREAM) in combination with data from the Atmospheric Chemistry Experiment – Fourier Transform Spectrometer and from ozone sondes. Using the high spatial and temporal resolution of M2-SCREAM, we analyze the daily evolution of southern polar ozone, HCl, N2O, and water vapor in dynamical flow-following coordinates relative to the location, size, and shape of the polar vortex. For vertically integrated stratospheric ozone we emphasize the importance of the wave-influenced geometry of the polar vortex and its vertical alignment. The ultimate purpose of this project is to contribute to the quantification of the speed of the Antarctic ozone recovery and associated uncertainties.

Krzysztof Wargan↗
DOE OSTI2025

Fast methods for multisite charge transfer processes. I. Constrained, state averaged CASSCF(1,n) and CASSCF(2n − 1,n) simulations

We design a dynamically weighted state-averaged constrained complete active space self-consistent field (DW-SA-cCASSCF) algorithm to treat electrons or holes moving between n molecular fragments (where n can be larger than 2). Within such a so-called eDSCn/hDSCn approach, we consider configurations that are mutually single excitations of each other, and we apply a generalized set of constraints to tailor the method for studying charge transfer problems. The constrained optimization problem is efficiently solved using a DIIS-SQP algorithm, thus maintaining computational efficiency. We demonstrate the method for a finite Su–Schrieffer–Heeger chain, successfully reproducing the expected exponential decay of diabatic couplings with distance. When combined with a gradient, the current extension immediately enables efficient nonadiabatic dynamics simulations of complex multi-state charge transfer processes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Atomistically resolved hot exciton relaxation dynamics in CdSe quantum dots: Experiment and theory

Semiconductor quantum dots (QDs) are well known to give rise to a quantum confined structure of excitons. Because of this quantum confinement, new physics of hot exciton relaxation dynamics arises. Decades of work using transient absorption (TA) spectroscopy have yielded initial simple observations, such as estimates of the cooling rate from single pump photon energy experiments. More detailed TA experiments employed variable pump photon energies to measure excitonic state-resolved transition rates. These TA measurements, usually the simplest form, have been employed to characterize QDs and their relaxation dynamics to this day. Yet, these TA measurements are fundamentally lacking in their ability to measure energy-resolved hot exciton cooling, which requires observation of the full cooling history through the real excitonic manifold. Here, we employ coherent multi-dimensional spectroscopy (CMDS) to perform an atomistically directed study of hot exciton cooling in CdSe QDs, revealing energy resolved relaxation dynamics. CMDS experiments are compared with simulations and prior TA measurements and simpler theories. Our findings reveal a hot exciton relaxation dynamics landscape. This relaxation dynamics landscape is a linear or sub-linear function of excess energy for different structures of QDs, with a strong size dependence. Our model simulations parameterized by the empirical pseudopotential model reproduces the experimental functional form and the dependence upon QD diameter and shell.

Atomistic simulations↗