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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 19 records
All sourcesNASA NTRSDOE OSTI
NASA NTRS1998

Molecular Processes in Comets

The research focused on molecular hydrogen and its response to ultraviolet radiation, photoelectron impact excitation and X-ray radiation and on the interpretation of the ultraviolet spectra of the Jupiter dayglow and auroras. A systematic effort was made to obtain reliable rate coefficients for rovibrational energy transfer of H2, particularly in collisions with hydrogen atoms. We carried out elaborate quantum-mechanical calculations of the scattering of H and H2 on what had been characterized as a reliable potential energy surface of the H3 molecular system. These calculations took into account reactive channels and rate coefficients for ortho-para transitions were obtained. Quantal calculations are too complex to be applied to all the possible rovibrational transitions and we turned to a semi-classical method. With it we calculated rate coefficients for transitions, reactive and non-reactive, for all the rovibrational levels. We carried out the calculations for three of the available H3 potential energy surfaces. We discovered an unexpected sensitivity of the rate coefficients for the non-reactive channels to the potential energy surface. This discovery stimulated more thorough investigations of the potential energy surface elsewhere and to the construction of a new surface. We have used it in further semi-classical calculations in work that will shortly be 2 completed and which, together with new quantum-mechanical calculations should comprise a set of reliable rate coefficients that can be used in discussions of H2 on the Jovian planets. We carried out a detailed study of the Jovian ultraviolet dayglow. There has been a long-running argument about the dayglow on Jupiter. There are two sources of excitation: fluorescence and photoelectron impact excitation. It had been argued that a third source "the electron glow" was needed to bring theory and observation into agreement. We believe we have shown conclusively that the third source is unnecessary. We have achieved a close quantitative agreement between the predicted spectrum arising from fluorescence and photoelectrons and the measured spectrum. We also demonstrated a method by which the presence of HD could be established observationary. Similar calculations were carried out of the ultraviolet spectra of the Jovian auroras. We again found close agreement. Indeed, the agreement was so detailed we were able to derive the temperature of the atmosphere. We found, contrary to the standard model of the time, a high temperature between 400 K and 600 K and established the presence of a significant temperature gradient. A large temperature gradient was indeed found by direct sampling with the Jupiter probe.

Dalgarno, A.↗
DOE OSTI2022

Emergent Behavior at the Calcite–Water Interface during Reactive Transport in a Simple Microfluidic Channel

Geochemical reactive transport processes in natural mineral-fluid systems may produce a wide array of emergent phenomena that are difficult to predict from basic principles and to reproduce in model systems. In this study, we present experimental results obtained from a simple microfluidic system with which we explored the consequences of reacting the calcite (104) cleavage surface with an acidic Pb-bearing solution (pH = 3.5, [Pb] total = 5 mM) as a function of flow rate. This system is relevant to passive remediation systems for Pb-rich acid mine drainage. We observed periodic banding in the amounts of Pb sorption at flow velocities ≥ 926 μm s -1 , where the band spacing was spatially correlated with the amount of calcite dissolution and the development of micropyramidal topography on the calcite (104) surface. The equivalent coverage of Pb deposited in these Pb-rich bands was at least several monolayers per unit cell, yet there was no evidence for precipitation of any secondary Pb phase implying incorporation of Pb within the near-surface calcite lattice. We also observed spatial variations in nucleation and growth of euhedral secondary Pb-carbonate minerals hydrocerusite and cerussite at flow rates ≤ 278 μm s -1 ,. These findings demonstrate potential for exploiting the rich phenomenology afforded by the interplay among transport phenomena and chemical kinetics in experimental systems designed to yield deeper insights into geochemical self-organization.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1984

Ion-molecule reactions in unsaturated hydrocarbons - Allene, propyne, diacetylene, and vinylacetylene

Ion-molecule reactions in allene, propyne, diacetylene, and vinylacetylene (1-buten-3-yne) have been studied at near-thermal energies by the technique of ion cyclotron resonance mass spectrometry. Rate coefficients and branching ratios are reported for the reactions of C3Hn(+) (n = 1-4) with allene and propyne and for the reactions of C4Hn(+) (n = 0-5) with diacetylene and vinylacetylene. Branching ratios are also given for the reactions of C4Hn(+), C5Hn and C6Hn(+) with propyne and for reactions of C6Hn(+) with diacetylene and vinylacetylene. More than 90 percent of the reactive channels lead to product ions having a larger carbon skeleton than the reactant ion. Evidence for ions with the same m/e ratio having differing reactivities was obtained for C3Hn(+), C6H7(+), and C7H7(+). Ion reaction sequences in allene and propyne were followed at higher pressures (0.0001 torr) to investigate secondary, tertiary, and higher order processes.

Anicich, V. G.↗
DOE OSTI2020

HCOOH Decomposition on Sub-Nanometer Pd 6 Cluster Catalysts: The Effect of Defective Boron Nitride Supports Through First Principles

The catalytic properties of a hexagonal boron nitride- (h-BN) supported Pd 6 sub-nanometer cluster in the context of formic acid (HCOOH) decomposition were studied by means of periodic Density Functional Theory (DFT) calculations. The effect of support defectivity – boron (h-B v N) and nitrogen (h-BN v ) monovacancies – on the competition between the formate (HCOO)- and carboxyl (COOH)-mediated decomposition pathways was analyzed. Defects are responsible for charge-transfer leading to a positively or negatively charged cluster, and open new reactive channels in which vacancy-mediated dehydrogenation pathways can occur. Pd 6 cluster reconstructions, induced by the adsorption of reaction intermediates and by the presence of monovacancies in the support, greatly stabilize the formation of CO from COOH, which could drastically decrease the selectivity towards hydrogen production. Here, a simplified descriptor-based analysis, based on selected thermochemical quantities calculated on charged cluster models, suggests that Pd 6 sub-nanometer clusters supported on pristine h-BN and h-BN v can be more selective than Pd 6 supported on defective h-B v N towards HCOOH dehydrogenation.

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

Selective Chemical Looping Combustion of Terminal Alkynes in Mixtures with Alkenes

The selective combustion of terminal alkynes in mixtures with alkenes is demonstrated during anaerobic reduction half-cycles on bulk bismuth oxide (Bi 2 O 3 ) as an approach to remove alkynes, which act as inhibitors in olefin polymerization. Bi 2 O 3 combusts phenylacetylene in styrene, 3-methylphenylacetylene in 3-methylstyrene, propyne in propylene, 1-hexyne in 1-hexene, and 1-octyne in 1-octene, with alkyne combustion selectivities exceeding 96%. Near unity reaction orders for hydrocarbon consumption during reduction half-cycles are consistent with combustion pathways initiated by rate-determining initial C–H activation, which drive selective alkyne combustion through intrinsic differences in the first-order rate constants for alkyne and alkene combustion rather than preferential adsorption of alkynes on Bi 2 O 3 surfaces. Computational assessments of initial C–H activation pathways for alkynes and alkenes on (010) α-Bi 2 O 3 surfaces using density functional theory illustrate that heterolytic transition states which form proton-carbanion pairs on Bi–O sites kinetically favor the activation of alkynes rather than alkenes due to differences in C–H bond acidity, and the barrier for heterolytic C–H activation is dictated in part by the sum of the molecular deprotonation energy and the energy to bind an R – carbanion to a Bi site in its transition-state geometry. Finally, these heterolytic reactivity channels during selective chemical looping combustion present novel routes for purifying olefin gas streams containing alkyne impurities.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1977

Flash photolysis resonance fluorescence investigation of the reaction of Cl/2P/ atoms with ClONO2

Rate constants for the removal of Cl(2P) atoms by homogeneous gas phase reaction with ClONO2 were measured using the flash photolysis resonance fluorescence technique at 224, 250, and 273 K. The values obtained have been used to derive the above Arrhenius equation. The uncertainties expressed are 95% confidence limits obtained using the statistical standard deviation of the individual rate constants plus a 15% additional estimated uncertainty attributed to difficulties in chlorine nitrate concentration measurements. The results indicate that destruction of chlorine nitrate by reaction with chlorine atoms is perhaps the least important of the atmospheric reactive channels, and is at least three orders of magnitude slower than calculated photodissociation rates at all stratospheric altitudes.

Kurylo, M. J.↗
NASA NTRS1978

Experiments concerning the laser-enhanced reaction between vibrationally excited O3 and NO

The enhancement in reaction rate between O3 and NO is studied for the case of O3 vibrationally excited by a CO2 laser. Chemiluminescence observations of a vibrationally excited and an electronically excited nitrogen dioxide reaction product provide information on the separate contributions to the overall reaction rate of these two reactive channels. The contribution of the stretching and bending modes of O3 to the reaction rate enhancement is also discussed. In addition, consideration is given to the nonreactive vibrational deactivation of vibrationally excited O3.

Hui, K.-K.↗
NASA NTRS1994

Rotational excitation of H2 in collision with H

Rate coefficients for the reactive processes of ortho-para conversion in which the j = 0 rotational level of molecular hydrogen is excited to the j = 1 and j = 3 level by impacts with hydrogen atoms are calculated for temperatures between 30 K and 1000 K using a fully converged complete close-coupled method. Rate coefficients are also obtained for the excitation from the j = 0 to the j = 2 rotational level and from the j = 1 to the j = 3 rotational level. The interference between the direct and reactive channels is taken into account as is the geometric phase resulting from the adiabatic separation of electronic and nuclear motion that generates the potential energy surface. Convenient analytic representations of the rate coefficients are presented.

Sun, Y.↗
NASA NTRS1994

New calculations on the ion-molecule processes C2H2(+) + H2 --> C2H3(+) + H and C2H2(+) + H2 --> C2H4+

New high-level quantum chemical calculations have been undertaken to understand the rates and mechanisms of the reactive and associative channels for the reactants C2H2(+) + H2. The reactive channel, which produces C2H3(+) + H, has been shown to be slightly endothermic, confirming earlier calculations at a somewhat lower level and in agreement with some recent experimental work. The associative channel, leading to C2H4+, has been shown to proceed via a transition state with negative energy relative to the reactants, so that association is predicted to be efficient. This result is in conflict with an earlier theoretical study but in agreement with low-temperature experimental measurements.

NASA Discipline Exobiology↗
NASA NTRS1971

Non-partial wave treatment of reactive and non-reactive scattering Coupled integral equation formalism.

Coupled integral equations are derived for the full scattering amplitudes for both reactive and nonreactive channels. The equations do not involve any partial wave expansion and are obtained using channel operators for reactive and nonreactive collisions. These coupled integral equations are similar in nature to equations derived for purely nonreactive collisions of structureless particles. Using numerical quadrature techniques, these equations may be reduced to simultaneous algebraic equations which may then be solved.

Hayes, E. F.↗
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↗
DOE OSTI2023

The Li + CaF → Ca + LiF chemical reaction under cold conditions

The calcium monofluoride (CaF) molecule has emerged as a promising candidate for precision measurements, quantum simulation, and ultracold chemistry experiments. Inelastic and reactive collisions of laser cooled CaF molecules in optical tweezers have recently been reported and collisions of cold Li atoms with CaF are of current experimental interest. In this paper, we report ab initio electronic structure and full-dimensional quantum dynamical calculations of the Li + CaF → LiF + Ca chemical reaction. The electronic structure calculations are performed using the internally contracted multi-reference configuration-interaction method with Davidson correction (MRCI + Q). An analytic fit of the interaction energies is obtained using a many-body expansion method. Furthermore, a coupled-channel quantum reactive scattering approach implemented in hyperspherical coordinates is adopted for the scattering calculations under cold conditions. Results show that the Li + CaF reaction populates several low-lying vibrational levels and many rotational levels of the product LiF molecule and that the reaction is inefficient in the 1–100 mK regime allowing sympathetic cooling of CaF by collisions with cold Li atoms.

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

Constructive Quantum Interference in Photochemical Reactions

Interferences emerge when multiple pathways coexist together, leading toward the same result. Here, we report a theoretical study for a reaction scheme that leads to constructive quantum interference in a photoassociation (PA) reaction of a 87 Rb Bose–Einstein condensate where the reactant spin state is prepared in a coherent superposition of multiple bare spin states. This is achieved by changing the reactive scattering channel in the PA reaction. As the origin of coherent control comes from the spin part of the wavefunction, we show that it is sufficient to use radio frequency (RF) coupling to achieve the superposition state. We simulate the RF coupling on a quantum processor (IBMQ Lima), and our results show that interferences can be used as a resource for the coherent control of photochemical reactions. The approach is general and can be employed to study a wide spectrum of chemical reactions in the ultracold regime.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1990

A time-dependent wave packet approach to atom-diatom reactive collision probabilities - Theory and application to the H + H2(J = 0) system

This paper describes a new approach to the study of atom-diatom reactive collisions in three dimensions employing wave packets and the time-dependent Schroedinger equation. The method uses a projection operator approach to couple the inelastic and reactive portions of the total wave function and optical potentials to circumvent the necessity of using product arrangement coordinates. Reactive transition probabilities are calculated from the state resolved flux of the wave packet as it leaves the interaction region in the direction of the reactive arrangement channel. The present approach is used to obtain such vibrationally resolved probabilities for the three-dimensional H + H2 (J = 0) hydrogen exchange reaction, using a body-fixed system of coordinates.

Neuhauser, Daniel↗
DOE OSTI2022

Improving the feasibility of economical proton-boron-11 fusion via alpha channeling with a hybrid fast and thermal proton scheme

The proton-boron-11 (p-B11) fusion reaction is much harder to harness for commercial power than the easiest fusion reaction, namely, the deuterium and tritium (DT) reaction. The p-B11 reaction requires much higher temperatures, and, even at those higher temperatures, the cross section is much smaller. However, as opposed to tritium, the reactants are both abundant and nonradioactive. It is also an aneutronic reaction, thus avoiding radioactivity-inducing neutrons. Economical fusion can only result, however, if the plasma is nearly ignited; in other words if the fusion power is at least nearly equal to the power lost due to radiation and thermal conduction. Because the required temperatures are so high, ignition is thought barely possible for p-B11, with fusion power exceeding the bremsstrahlung power by only around 3%. We show that there is a high upside to changing the natural flow of power in the reactor, putting more power into protons, and less into the electrons. This redirection can be done using waves, which tap the alpha particle power and redirect it into protons through alpha channeling. Using a simple power balance model, we show that such channeling could reduce the required energy confinement time for ignition by a factor of 2.6 when energy is channeled into thermal protons, and a factor of 6.9 when channeled into fast protons near the peak of the reactivity. Furthermore, alpha channeling could dramatically improve the feasibility of economical p-B11 fusion energy.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
NASA NTRS2004

Lunar and Planetary Science XXXV: Ancient Mars Water and Landforms

Titles in this section include: 1) Giant Lowland Polygons: Relics of an Ancient Martian Ocean? 2) Lake Shorelines: Earth Analogs for Hypothesized Martian Coastal Features; 3) Complex Evolution of Paleolacustrine Systems on Mars: An Example from the Holden Crater; 4) Geomorphology and Hydraulics of Ma'adim Vallis, Mars, During a Noachian/Hesperian Boundary Paleoflood; 5) Geologic Evolution of Dao Vallis, Mars; 6) Advances in Reconstructing the Geologic History of the Chryse Region Outflow Channels on Mars; 7) Ravi Vallis, Mars - Paleoflood Origin and Genesis of Secondary Chaos Zones; 8) Walla Walla Vallis and Wallula Crater: Two Recently Discovered Martian Features Record Aqueous History; 9) Tharsis Recharge: a Source of Groundwater for Martian Outflow Channels; 10) Factors Controlling Water Volumes and Release Rates in Martian Outflow Channels; 11) Significance of Confined Cavernous Systems for Outflow Channel Water Sources, Reactivation Mechanisms and Chaos Formation; 12) Systematic Differences in Topography of Martian and Terrestrial Drainage Basins; 13) Waves on Seas of Mars and Titan: Wind-Tunnel Experiments on Wind-Wave Generation in Extraterrestrial Atmospheres.

Source record↗
DOE OSTI2025

The Role of Interfaces and Charge for Chemical Reactivity in Microdroplets

A wide variety of reactions are reported to be dramatically accelerated in aqueous microdroplets, making them a promising platform for environmentally clean chemical synthesis. However, to fully utilize the microdroplets for accelerating chemical reactions requires a fundamental understanding of how microdroplet chemistry differs from that of a homogeneous phase. Here, in this work, we provide our perspective on recent progress to this end, both experimentally and theoretically. We begin by reviewing the many ways in which microdroplets can be prepared, creating water/hydrophobic interfaces that have been frequently implicated in microdroplet reactivity due to preferential surface adsorption of solutes, persistent electric fields, and their acidity or basicity. These features of the interface interplay with specific mechanisms proposed for microdroplet reactivity, including partial solvation, possible gas phase channels, and the presence of highly reactive intermediates. We especially highlight the role of droplet charge and associated electric fields, which appears to be key to understanding how certain reactions, like the formation of hydrogen peroxide and reduced transition metal complexes, are thermodynamically possible in microdroplets. Lastly, we emphasize opportunities for theoretical advances and suggest experiments that would greatly enhance our understanding of this fascinating subject.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗