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At least 523 records · Page 29
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Visualization of in-situ chemical flow through sand using neutron radiography

Chemical movement through soil is an important process in agriculture and ecology. Observing the spatial and temporal dynamics of these processes using conventional chemical ecology methods requires techniques that are destructive and/or lack resolution. Neutron radiography has the capability to allow chemical motion through sand/soil to be tracked with high spatial and temporal resolution, and we show that it allows for the motion of hydrophobic and hydrophilic chemicals to be distinguished. This technique can have an important impact on introducing neutron radiography to a wider community and into our understanding of chemical communication dynamics between plants and movement of applied chemicals in agricultural soils.

MORRIS, KATHRYN [Xavier University]↗
NASA NTRS1977

Chemical Evolution and the Origin of Life: Bibliography 1975

This bibliography is the sixth annual supplement to the comprehensive bibliography on the same subject which was published in Space Life Sci.We would like to draw attention to a recently published cumulative bibliography on this same subject: Biochemical Origin of Life: Chemistry and Life. Soil and Water and Its Relationship to Origin of Life. MR - Studies of Prebiotic Polypeptides. Energy, Matter, and Life. Prospects for the Future Orientation of Scientific Research. Photochemical Formation of Self Sustaining Coacervates. Photochemical Formation of Self-Sustaining Coacervates. Comparative Study of Abiogenesis of Cysteine and Other Amino Acids Catalyzed by Various Metal Ions. Protein Structure and the Molecular Evolution of Biological Energy Conversion. Origin of Life. Clues from Relations Between Chemical Compositions of Living Organisms and Natural Environments. Shock Synthesis of Amino Acids II.', Origins of Life 6(1-2). Dynamics of the Chemical Evolution of Earth's Primitive Atmosphere. The Mechanisms of Amino Acids Synthesis by High Temperature Shock-Waves. Theory of Chemical Evolution. Physical Foundations of Probability of Biogenesis.

West, Martha W.↗
DOE OSTI2024

17 O NMR Spectroscopy Reveals CO 2 Speciation and Dynamics in Hydroxide-Based Carbon Capture Materials

Carbon dioxide capture technologies are set to play a vital role in mitigating the current climate crisis. Solid-state 17 O NMR spectroscopy can provide key mechanistic insights that are crucial to effective sorbent development. In this work, we present the fundamental aspects and complexities for the study of hydroxide-based CO 2 capture systems by 17 O NMR. We perform static density functional theory (DFT) NMR calculations to assign peaks for general hydroxide CO 2 capture products, finding that 17 O NMR can readily distinguish bicarbonate, carbonate and water species. However, in application to CO 2 binding in two test case hydroxide-functionalised metal-organic frameworks (MOFs) – MFU-4l and KHCO 3 -cyclodextrin-MOF, we find that a dynamic treatment is necessary to obtain agreement between computational and experimental spectra. We therefore introduce a workflow that leverages machine-learning force fields to capture dynamics across multiple chemical exchange regimes, providing a significant improvement on static DFT predictions. In MFU-4l, we parameterise a two-component dynamic motion of the bicarbonate motif involving a rapid carbonyl seesaw motion and intermediate hydroxyl proton hopping. For KHCO 3 -CD-MOF, we combined experimental and modelling approaches to propose a new mixed carbonate-bicarbonate binding mechanism and thus, we open new avenues for the study and modelling of hydroxide-based CO 2 capture materials by 17 O NMR.

NMR spectroscopy↗
DOE OSTI2025

Iodine recombination in xenon solvent: Clusters in the gas to liquid-like state transition

Supercritical fluids (SCFs) have attracted significant attention as solvents for chemical reactions due to their unique properties, such as high diffusivity, low viscosity, and tunable solvation properties. These properties profoundly influence reaction kinetics and are often attributed to the formation of molecular clusters within SCFs. To study the effect of supercritical solvent on chemical reactivity and dynamics of reactions, one needs to understand the dynamics of clusters in supercritical fluid. Extensive experiments on the photodissociation and recombination of iodine in supercritical fluids served as a model system for understanding these effects. Experimental studies have been complemented by theoretical and computational investigations, which mostly employ Monte Carlo or empirical molecular dynamics simulations. However, computational studies using non-reactive force fields and ab initio approaches present challenges in capturing reactive processes at larger scales within supercritical fluids. Here, in this work, we developed the ReaxFF parameters by training against quantum mechanics data. ReaxFF reactive force field based molecular dynamics simulations were performed, studying the dynamics of a xenon solvent and cage effect at different thermodynamic conditions for the iodine recombination reaction. We show that the conditions near the critical point are the optimal conditions to study the cage effect. We show that the average lifetime of xenon clusters ranging between 5 and 11 ps is comparable to iodine geminate recombination. Our simulation results of iodine recombination in xenon solvent demonstrate the higher probability of iodine molecule formation in the presence of xenon clusters. Finally, we show that the supercritical condition exhibits the highest recombination rate for iodine atoms.

Cage effect↗
NASA NTRS1992

The spectroscopy of the atmosphere using far-infrared emission experiment (SAFIRE)

The goal of the SAFIRE experiment is to improve understanding of the middle-atmospher ozone distribution by conducting and analyzing global-scale measurements of important chemical, radiative and dynamical processes, including coupling among these processes and atmospheric regions. This will be accomplished by observing vertical profiles of temperature and key gases in the main chemical families. A detailed listing of SAFIRE measurements, including sepctral ranges, altitude ranges, IFOV, spatial and temporal resolution, latitude coverage and estimated precision is provided. The temperature, O3, CH4, and H2O observations will be useful for deriving and studying dynamical quantities such as geopotential height, potential vorticity, balanced winds and Eliassen-Palm fluxes. The SAFIRE observations will provide important data for study of chemistry, dynamics and transport processes. This experiment was conceived in response to a need for simultaneous measurements of odd hydrogen gases. These include gases such as OH, HO2, and atomic oxygen, which have not been observed by past satellite experiments and which will not be measured by any of teh Upper Atmosophere Reserach Satellite (UARS) experiments to be launched in 1991.

Russell, J. M., III↗
DOE OSTI2022

Binding kinetics of harmonically confined random walkers

Diffusion-mediated binding of molecules under the influence of discrete spatially confining potentials is a commonly encountered scenario in systems subjected to explicit fields or implicit fields arising from tethering restraints. Here, in this work, we derive analytical expressions for the mean binding time of two random walkers geometrically confined by means of two harmonic potentials in one- and two-dimensional systems, which show excellent agreement with Brownian dynamics simulations. As a demonstration of its utility, we use this theory to maximize the communication speed in existing DNA walkers, obtaining quantitative agreement with previously reported experimental findings. The analytical expressions derived in this paper are broadly applicable to diverse systems, providing ways to characterize communication processes and optimize the rate of signal propagation for sensing and computing applications at the nanoscale.

36 MATERIALS SCIENCE↗
NASA NTRS1992

A preliminary model of the coma of 2060 Chiron

We have included gravity in our fluid dynamic model with chemical kinetics of dusty comet comae and applied it with two dust sizes to 2060 Chiron. A progress report on the model and preliminary results concerning gas/dust dynamics and chemistry is given.

Boice, Daniel C.↗
NASA NTRS1991

Dynamical conditions of dense clumps in dark clouds - A strategy for elucidation

Chemical considerations and simplified dynamical modeling suggest that dark cloud cores may be incessantly evolving such that the time spent at high core densities decreases as the density increases. After reaching a high density, gravitationally contracting dark cloud cores may either form stars or expand to states of lower densities. Cloud mass and initial density are amongst the factors that may control the evolutionary fate of the core. This view is diametrically opposite of the common belief that dense cores may be in near mechanical equilibrium. Mutually consistent end-to-end modeling of the spectral line profiles and intensities is needed to discern the reality.

Prasad, Sheo S.↗
DOE OSTI2026

Fundamental chemical physics revealed by scattering reactive open-shell atoms from surfaces

The dynamics of reactive atoms at surfaces are centrally important to areas such as heterogeneous catalysis, corrosion, materials degradation in extreme environments, and plasma etching. Remarkably detailed understanding of dynamical processes at surfaces has been extracted from scattering molecules and inert atoms under well-defined conditions. However, traditional techniques for generating beams of reactive atoms often result in impure mixtures, broad energy distributions, and poorly defined contributions of metastable electronically excited atoms. In this perspective article, we review the state-of-the-art in reactive atom surface scattering with a focus on experiments performed under controlled conditions on well-defined surfaces. We highlight a new technique for controlled state-to-state scattering of polyelectronic atoms from surfaces, based on vacuum ultraviolet photolysis and state-selective ion imaging. The new capabilities provide an avenue for research into the underexplored area of excited state and spin selective chemical dynamics at surfaces.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
NASA NTRS1985

Direct numerical simulations of a reacting mixing layer with chemical heat release

In order to study the coupling between chemical heat release and fluid dynamics, direct numerical simulations of a chemically reacting mixing layer with heat release are performed. The fully compressible equations as well as an approximate set of equations that is asymptotically valid for low-Mach-number flows are treated. These latter equations have the computational advantage that high-frequency acoustic waves have been filtered out, allowing much larger time steps to be taken in the numerical solution procedure. A detailed derivation of these equations along with an outline of the numerical solution technique is given. Simulation results indicate that the rate of chemical product formed, the thickness of the mixing layer, and the amount of mass entrained into the layer all decrease with increasing rates of heat release.

Mcmurtry, P. A.↗
DOE OSTI2023

Probing reaction channels via reinforcement learning

Abstract Chemical reactions are dynamical processes involving the correlated reorganization of atomic configurations, driving the conversion of an initial reactant into a result product. By virtue of the metastability of both the reactants and products, chemical reactions are rare events, proceeding fleetingly. Reaction pathways can be modelled probabilistically by using the notion of reactive density in the phase space of the molecular system. Such density is related to a function known as the committor function, which describes the likelihood of a configuration evolving to one of the nearby metastable regions. In theory, the committor function can be obtained by solving the backward Kolmogorov equation (BKE), which is a partial differential equation (PDE) defined in the full dimensional phase space. However, using traditional methods to solve this problem is not practical for high dimensional systems. In this work, we propose a reinforcement learning based method to identify important configurations that connect reactant and product states along chemical reaction paths. By shooting multiple trajectories from these configurations, we can generate an ensemble of states that concentrate on the transition path ensemble. This configuration ensemble can be effectively employed in a neural network-based PDE solver to obtain an approximation solution of a restricted BKE, even when the dimension of the problem is very high. The resulting solution provides an approximation for the committor function that encodes mechanistic information for the reaction, paving a new way for understanding of complex chemical reactions and evaluation of reaction rates.

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

The Role of Lidars in Global Change Research

Recent research has solidified a view of the Earth as a global scale interactive system with complex chemical, physical, biological, and dynamical processes that link the ocean, atmosphere, land, and marine terrestrial living organisms. An important aspect of Earth System Science studies in the future is the need to observe simultaneously the physical, chemical, biological, and dynamical processes involved in highly coupled phenomena such as those mentioned. Lidars operating from the surface, aircraft, and satellites provide a powerful observational technique to study the processes and observe trends important to global change. Lidar observations have already played important roles in helping understand processes controlling stratospheric ozone and aerosols, tropospheric clouds, water vapor, ozone, gaseous pollutants, and aerosols, and winds and temperatures throughout the atmosphere. In this paper the author reviews the science of global change and highlights the potential roles for lidar in studying the Earth system.

Prinn, Ronald G.↗
DOE OSTI2020

Modeling Molecules under Pressure with Gaussian Potentials

The computational modeling of molecules under high pressure is a growing research area that augments experimental high-pressure chemistry. Here, a new electronic structure method for modeling atoms and molecules under pressure, Gaussians On Surface Tesserae Simulate HYdrostatic Pressure (GOSTSHYP) approach, is introduced. In this method, a set of Gaussian potentials is distributed evenly on the van der Waals surface of the investigated chemical system, leading to a compression of the electron density and the atomic scaffold. Since no parameters other than pressure need to be specified, GOSTSHYP allows straightforward geometry optimizations and ab initio molecular dynamics simulations of chemical systems under pressure for nonexpert users. In this work, calculated energies, bond lengths, and dipole moments under pressure fall within the range of established computational methods for high-pressure chemistry. A Diels-Alder reaction and the cyclotrimerization of acetylene showcase the ability of GOSTSHYP to model pressure-induced chemical reactions. The connection to mechanochemistry is pointed out.

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

Femtosecond ultraviolet laser absorption spectroscopy for simultaneous measurements of temperature and OH concentration

This Letter reports a femtosecond ultraviolet laser absorption spectroscopy (fs-UV-LAS) for simultaneous in situ measurements of temperature and species. Here, this fs-UV-LAS technique was demonstrated based on X 2 Π-A 2 Σ + transitions of OH radicals near 308 nm generated in low temperature plasmas and flames. The fs-UV-LAS technique has revealed three major diagnostic benefits. First, a series of absorption features within a spectral bandwidth of ~3.2 nm near 308 nm were simultaneously measured and then enabled simultaneous multi-parameter measurements with enhanced accuracy. The results show that the temperature and OH concentration could be measured with accuracy enhanced by 29–88% and 58–91%, respectively, compared to those obtained with past two-narrow-line absorption methods. Second, an ultrafast time resolution of ~120 picoseconds was accomplished for the measurements. Third, due to the large OH X 2 Π-A 2 Σ + transitions in the UV range, a simple single-pass absorption with a 3-cm path length was allowed for measurements in plasmas with low OH number density down to ~2 × 10 13 cm –3 . Also due to the large OH UV transitions, single-shot fs absorption measurements were accomplished in flames, which was expected to offer more insights into chemically reactive flow dynamics.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
NASA NTRS1993

Theoretical studies in interstellar cloud chemistry

This final report represents the completion of the three tasks under the purchase order no. SCPDE5620,1,2F. Chemical composition of gravitationally contracting, but otherwise quiescent, interstellar clouds and of interstellar clouds traversed by high velocity shocks, were modeled in a comprehensive manner that represents a significant progress in modeling these objects. The evolutionary chemical modeling, done under this NASA contract, represents a notable advance over the 'classical' fixed condition equilibrium models because the evolutionary models consider not only the chemical processes but also the dynamical processes by which the dark interstellar clouds may have assumed their present state. The shock calculations, being reported here, are important because they extend the limited chemical composition derivable from dynamical calculations for the total density and temperature structures behind the shock front. In order to be tractable, the dynamical calculations must severely simplify the chemistry. The present shock calculations take the shock profiles from the dynamical calculations and derive chemical composition in a comprehensive manner. The results of the present modeling study are still to be analyzed with reference to astronomical observational data and other contemporary model predictions. As far as humanly possible, this analysis will be continued with CRE's (Creative Research Enterprises's) IR&D resources, until a sponsor is found.

Chiu, Y. T.↗
DOE OSTI2024

Modeling prebiotic chemistries with quantum accuracy at classical costs

Molecular Dynamics (MD) simulations using classical force-fields are commonly employed in numerous scientific investigations. However, many natural processes involve bond breaking and quantum forces. This complexity is compounded by the presence of multiple competing length and timescales. For example, accurately modeling the thermodynamics and dynamics of a chemical reaction requires accounting for the concerted movements of numerous solvent molecules and ions with their own fast or slow timescales. While widely used static Density Functional Theory (DFT) calculations at 0 temperature can be beneficial for such investigations, they do not account for dynamics, and lack precision in describing the molecular environments. They particularly fail at correct, rigorous treatments of finite-temperature fluctuations, and thus generalization to experimentally relevant conditions. In PNAS Benayad et al develop a scalable, generalizable approach for designing Neural Network Potentials (NNPs) that can handle chemical reactivity in solvated systems with quantum accuracy at classical costs. Specifically, they study phosphoester bond formation and rupture, which is fundamentally relevant to the Phosphorus-Oxygen bond formation central to life, and especially for the RNA world hypothesis. The framework developed here has the potential to generalize to different chemical reactions of energy and biological relevance.

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

Long-range exciton diffusion in molecular non-fullerene acceptors

Abstract The short exciton diffusion length associated with most classical organic semiconductors used in organic photovoltaics (5-20 nm) imposes severe limits on the maximum size of the donor and acceptor domains within the photoactive layer of the cell. Identifying materials that are able to transport excitons over longer distances can help advancing our understanding and lead to solar cells with higher efficiency. Here, we measure the exciton diffusion length in a wide range of nonfullerene acceptor molecules using two different experimental techniques based on photocurrent and ultrafast spectroscopy measurements. The acceptors exhibit balanced ambipolar charge transport and surprisingly long exciton diffusion lengths in the range of 20 to 47 nm. With the aid of quantum-chemical calculations, we are able to rationalize the exciton dynamics and draw basic chemical design rules, particularly on the importance of the end-group substituent on the crystal packing of nonfullerene acceptors.

14 SOLAR ENERGY↗